Reaction products of two chlorides of certain metals with borate esters



United States Patent US. Cl. 260-4295 16 Claims ABSTRACT OF THE DISCLOSURE This invention relates to products of unknown complex chemical structures prepared by reacting a substantially anhydrous borate ester such as trimethyl borate, triethyl borate, tripropyl borate, trihexyl borate, trihexylene glycol biborate, tri(m, p, cresyl) borate, and trimethoxyboroxine with a chloride of a first metal selected from the group consisting of Ti(IV), Zr(IV), Hf(IV), Sn(IV), Al(III), Fe(III), Ga(III), In(III), Mo(V), Nb(V), Ta(V), and W(VI) in a molar ratio of at least 0.33 mole of the selected borate ester for each mole of the chloride of the selected metal in an inert diluent, such as the selected borate ester, methylene chloride, chloroform, and carbon tetrachloride, at a temperature between room temperature and about 200 C. until the reaction mixture ceases to give off organic chloride thereby forming a liquor comprising the diluent and a compound of complex chemical structure comprising the selected metal, boron, carbon, hydrogen, chlorine, and oxygen. Then adding to said liquor the chloride of a second metal selected from the above group in a molar quantity not greater than that of the chloride of the first selected metal to react with said complex compound at a temperature between room temperature and about 200 C. thereby forming a second compound of complex chemical structure. The second compound of complex structure is isolated by removing volatile material from the reaction mixture by evaporation. The product can be applied to surfaces such as glass and cellulosic fabrics and marked water repellency develops.

This application is a continuation-in-part of my copending application Ser. No. 670,417, filed Sept. 25, 1967, now abandoned which was a division of my copending application Ser. No. 670,419, filed Sept. 25, 1967, Pat. No. 3,455,976, filed July 15, 1969.

This invention relates to products of unknown chemical structure prepared by reacting certain substantially anhydrous borate esters with a chloride of a first metal selected from the group consisting of Ti(IV), Zr(IV), Hf(IV), Sn(IV), Al(III), Fe(III), Ga(III), 'In(III), Mo(V), Ta(V), and W(VI) to form a compound of complex chemical structure and then reacting said compound with the chloride of a second metal selected from said group to form a second compound of complex chemical structure comprising the two selected metals, boron, carbon, hydrogen, chlorine and oxygen.

My above mentioned copending application Ser. No. 670,419, filed Sept. 25, 1967, discloses the preparation of highly useful products of complex chemical structure which are the reaction products of trimethyl borate with the chloride of a metal selected from the group consisting of Ti(IV), Zr(IV), Hf(IV), Al(III), Fe(III), Sn(IV), Mo(V), Nb(V), Ta(V), W(VI) and mixtures of such chlorides. While it is preferred to employ trimethyl borate, it may be replaced by other borate esters, such as triethyl borate, tripropyl borate, tributyl borate, trihexyl 3,515,738 Patented June 2, 1970 borate, trihexylene glycol biborate, tri(m, p, cresyl borate and mixtures thereof or a mixture of one or more of such borates with trimethyl borate. I have now found that trimethoxy boroxine may also replace trimethyl borate and that GaCl and InCl are operative metal chlorides.

As disclosed in my copending application Ser. No. 670,419, filed Sept. 25, 1967, in forming these products of unknown complex chemical structure using trimethyl borate, the substantially anhydrous chloride of the selected metal is mixed with substantially anhydrous trimethyl borate in a molar ratio of at least about 0.33 mole of borate ester for each mole of the chloride of the selected metal, preferably, in a substantially anhydrous inert diluent, such as methylene chloride, chloroform, carbon tetrachloride, or an excess of the trimethyl borate. The reactions may be carried out between room temperature and about 120 C. The order of addition of the reagents is not critical. Thus, the metal chloride may be added to the boron ester, or the boron ester may be added to the metal chloride, or both may be added simultaneously to the reaction zone.

In the case of the very reactive combinations of reagents, such as titanium tetrachloride or ferric chloride with trimethyl borate, the reactions start immediately at room temperature and the temperature of the reaction mixture rises slightly with methyl chloride being given off. In the case of less reactive combinations of reagents, it is often necessary to heat the reagents mildly, for example, to the boiling point of methylene chloride (40 C.) or trimethyl borate (6768 C.), or in a few cases to temperatures as high as -120 C.

When methyl chloride ceases to be given off the reaction is complete and the desired reaction product may be isolated by evaporation of volatile material, such as the diluent or excess reagent. This may be accomplished by applying a vacuum to the reaction vessel while gently heating. In some cases, the reaction product is highly soluble in the reaction medium, therefore, stronger heating under vacuum is required to remove the volatile material. In general, temperatures not over C. under a final vacuum of 120 mm. of mercury are sufiicient to remove the volatile material.

The method for reacting the chlorides of the previously mentioned group of metals with other borate esters, such as triethyl borate, tripropyl borate, tributyl borate, trihexyl borate, trihexylene glycol biborate, tri(m, p, cresyl borate, trimethoxy boroxine, and mixtures thereof or a mixture of one or more of such borates with trimethyl borate is similar to that described for the reaction With trimethyl borate. With these borate esters, however, the reactions are, in general, considerably slower and temperatures up to about 200 C. may be used to obtain reasonable reaction rates. Since the boiling points of the organic chloride by-products are considerably higher than methyl chloride, they must be distilled or evaporated from the reaction products by heating the reaction mixture either at atmospheric or reduced pressure.

In addition to the inert diluents previously mentioned these complex reactions may also be carried out in aliphatic hydrocarbons, such as petroleum ether, hexane, heptane, and cyclohexane. However, the reactions proceed much more slowly in these diluents and, therefore,

are not preferred.

The composition of the complex reaction products of the borate esters and metal chlorides appear to vary with the molar ratios of the borate esters to metal chloride as indicated by the amount of organic chloride given off. As the molar ratio of borate ester to metal chloride increases, the solubility and the acidity decreases.

These reaction products appear to be polymeric in nature and very complex in chemical structure. While I do not wish to be limited to any theory, there is evidence that one or more metal-oxygenboron bonds are formed in these reactions leading to materials which in their simplest form any have the following general formula:

and polymers formed by coordination cross linking thereof, where M represents the metal, n plus in equals the valence of the metal and R is selected from alkyl, aryl or the connecting structure of the boroxine group.

These complex products are soluble to a greater or lesser extent in water giving acidic solutions. When freshly prepared in methylene chloride they are at least slightly soluble in methylene chloride and also in one or more of the solvents chloroform, carbon tetrachloride, acetone, and glycol ethers, such as monomethyl ethylene glycol and dimethyl ethylene glycol ethers. Upon standing or drying, a product is formed which is insoluble in non-polar organic solvents. When dissolved in water or alcohol and applied to surfaces such as glass and cellulosic fabrics, and the solvent evaporated, marked water repellency develops. The water repellency can be enhanced by washing in a 1 percent solution of soap, rinsing and drying.

When reacting a mixture of chlorides of selected metals with a borate ester, at least about 0.33 mole of the selected borate is used for each sum of the molar proportions of the chlorides of the selected metals totaling one mole.

When producing a complex product prepared by the reaction of the chlorides of at least two selected metals with a borate ester, it is often preferable to react one of the metal chlorides with the borate completely as previously described but without isolating the complex reaction product. The chloride of another selected metal, in a molar quantity not greater than the molar quantity of the chloride of the first selected metal, then may be added to the reaction liquor and be reacted with the previously formed complex reaction product at a temperature between room temperature and about 200 C. After the second reaction has been completed, as indicated when organic chloride ceases to be given off, volatile material is removed by evaporation to isolate the second complex reaction prouct. This method is particularly advantageous when it is desired to react a very reactive metal chloride, such as titanium tetrachloride or ferric chloride, and a less reactive metal chloride with a borate ester. This method also makes possible the reaction of a borate ester with one or more of the chlorides of the metals of the group previously mentioned together with the chloride of a metal which alone does not react with a borate ester, such as silicon tetrachloride.

While I do not wish to be limited to any theory, there is evidence that the reaction products mentioned in the last previous paragraph may be polymers which are cross linked by coordination and which contain a plurality of linkages as represented by the following formula where M and N are different metals and the number of bonds shown correspond to the selected metals.

These complex products prepared with trimethyl borate and the chlorides of two or more metals still contain unreacted chlorine atoms which are reactive toward many organic compounds which contain a reactive hydrogen atom, such as amino, hydroxyl, or carboxyl groups. They may also react with further amounts of trimethyl borate if reactive chlorine atoms remain on the metal. The reaction product of aluminum trichloride, methyl borate and silicon tetrachloride exhibits a pinkish white fluorescence when irradiated with ultra violet of 3650 A. The products of the invention are slightly soluble in methylene chloride and most are soluble to some extent in highly polar solspecific examples:

EXAMPLE 1 This experiment was carried out in equipment comprising a stirred reaction flask which was fitted with an addition funnel, thermometer and reflux condenser. The

reflux condenser in turn was connected to an empty safety trap, then to a water scrubber and then to a gas meter.

grams of titanium tetrachloride (0.5 mole) was first reacted with 104 grams of trimethyl borate (1 mole) in 200 grams of methylene chloride. The reaction proceeded rapidly at 2644 C. About 1 mole of methyl chloride was given off indicating that about two of the chlorine atoms in the TiCl had reacted with the trimethyl borate to release CH Cl. When the reaction was completed, 42'

grams of SiCl (0.25 mole) was added over a period of about 30 minutes. An immediate reaction occurred and methyl chloride was given off. This reaction was continued for about 5 hours and about 0.8 mole of methyl chloride was given off. When the Sick, was first added to the clear amber solution of the reaction of TiCh, and trimethyl borate, yellow solids were formed which dissolved as the reaction progressed. An additional 200 grams of CHgCl was added to the reaction mixture at the end of the reaction. Almost all of the solids dissolved. The methylene chloride was removed from the product by vacuum evaporation. There was recovered about 157 grams of yellow solids which rapidly dissolved in water with effervescence and evolution of heat. The yellow solids softened and became rubbery over a temperature range of about 70 C. As the temperature was raised over 100 C., volatile material was evolved and the solids turned white and became much less soluble in water.

Elemental analysis of the product showed (percent): Ti, 15.6; Si, 3.3; Cl, 27.5; B, 8.2; C, 7.2; H, 2.7; O (by difference), 25.5.

A 1% aqueous solution of this product was applied to glass fabric and dried. A marked delustering occurred- Then the fabric was washed in a 1% aqueous solution, rinsed and dried. Excellent water repellency developed.

EXAMPLE 2 Sixty-seven grams (0.5 mole) of dry, ground AlCl was suspended in 400 g. of dry CH C1 in a 1-liter flask. To this was added 104 grams (1 mole) of methyl borate over a period of about 25 minutes. The reaction mixture was heated for about another 3 hours. About 0.75 mole of methyl chloride was evolved. Then 84 grams of SiCl was added to the flask with stirring over a period of about 30 minutes. The reaction mixture was heated to 4042 C.

for about 28 hours. Another 0.75 mole of methyl chloride 7 was evolved. The product was a white finely divided solid which was isolated by filtering from the methylene chloride and drying at about 75 C. in a vacuum oven. Total recovery was about g. of white solids.

A 1% aqueous solution of this product wasvery sub- I stantitive to glass fabric. A dip of the fabric in 1% solu- 7 tion followed by a squeeze through lIOllS to give about 100% wet pick up, then ironed dry gave a fabric which was permanently stiflfened in a way that starch stiifens cotton fabric. This stiifening resisted washing out even in soap solutions. When rinsed in a soap solution, outstanding water repellency developed.

EXAMPLE 3 As in previously described examples 0.5 mole of TiCl, was added to 1 mole of methyl borate diluted with 200 grams of methylene chloride. When about 1 mole of CH Cl had been evolved, a deep yellow-brown clear solution remained. To a separate stirred reaction flask fitted with a dropping funnel, thermometer, reflux condenser and Dry Ice trap, was charged 300 ml. of methylene chloride and 68.5 grams (0.25 mole) of MoCl The MoCl dissolved to form a dark blood red solution. The reaction product of TiCl, and methyl borate was charged to the dropping funnel. This solution was added to the MoCl -methylene chloride solution in the reaction flask over a period of minutes. Methyl chloride again was rapidly evolved, heat was evolved and the reaction mixture turned brown and finally black. The reaction product was isolated by vacuum evaporation of the methylene chloride to leave about 2.22 grams of black granular solid product which had the following analysis (percent): Ti=l3.l, Mo=9.0, 01:29.1, B=4.7, OCH =26.8.

EXAMPLE 4 This experiment was carried out exactly as in the previous example except that 0.25 mole of WCl suspended in 300 ml. methylene chloride was reacted with the performed reaction product of 0.5 mole TiCl and 1 mole -B(OCH in 200 grams methylene chloride. Again heat and methyl chloride were evolved from the reaction. The color of the reaction mass changed from dark brown to rusty red and finally to a dark olive green suspension. After isolation the product was analyzed and found to contain (percent): Ti-=13, W=16, Cl=24.9, B=5.2, OCH =22.5.

EXAMPLE 5 In this experiment 0.25 mole of MoCl was reacted with 0.75 mole of B(OCH in 500 ml. methylene chloride. About 0.75 mole of methyl chloride was evolved. When this part of the reaction was completed, 0.25 mole of WC1 powder was added in two equal increments. A vigorous reaction took place with each addition of WCl About 1 mole of methyl chloride was evolved. The final reaction mixture was a tan slurry. When the liquids were removed by vacuum evaporation there remained about 162 grams of olive green finely divided powder. This product was photochromic turning a deep blue black when exposed to light and reverting to the olive green color in the dark. Analysis of the product showed (percent): Mo=11.4, W=3l.4, Cl=l9.l, B=4.4, OCH =9.7.

EXAMPLE 6 0.5 mole of FeCl;, dissolved and suspended in 200 grams of methylene chloride was reacted with 1 .mole of B(OCH at -42 C. over a period of 1 hour and minutes. About 0.5 mole of methyl chloride was evolved. Then 0.25 mole of SiCl was added over a perriod of 20 minutes. Methyl chloride was slowly evolved and continued to be given off over a period of 16 hours. When the reaction was complete the product was isolated by vacuum evaporation of the liquid products leaving a yellow-brown solid. Analysis showed (percent): Fe=l9.3, Si=3.3, B=3.8, Cl=29.1. The ratio of Fe to Si was 3 to l and the ratio of B to Cl was 34- to 7.

In my copending application Ser. No. 670,419, filed Sept. 25, 1967 I have claimed methods for producing compounds of unknown complex chemical structure by reacting borate esters such as trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, trihexyl borate, trihexylene glycol borate, and tri(m, p, cresyl) borate with a chloride of a metal selected from the group consisting of Ti(IV), Zr(IV), Hf(IV), Sn(IV), and Si(IV) together with the complex compounds formed thereby.

In my copending application Ser. No. 670,450, filed Sept. 25, 1967, and now US. Pat. No. 3,457,289 I have claimed methods for producing compounds of unknown complex chemical structure by reacting borate esters selected from the group consisting of trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, trihexyl borate, trihexylene glycol biborate, and tri(m, p, cresyl borate with a chloride of a metal selected from 6 the group consisting of Al(III), Fe(III), and Cu(I) together with the complex compounds formed thereby.

In my copending application Ser. No. 670,449, filed Sept. 25, 196-7, and now US. Pat. No. 3,462,469 I have claimed methods for producing compounds of unknown complex chemical structure by reacting borate esters such as trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, trihexyl borate, trihexylene glycol biborate, and tri(m, p, cresyl) borate with a chloride of a metal selected from the group consisting of Mo(V), Nb(V), Ta(V) and W(VI) together with the complex compounds formed thereby.

In my copending application Ser. No. 670,418, filed Sept. 25, 1967, and now abandoned I have claimed methods -for producing compounds of unknown complex chemical structure by reacting borate esters such as trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, trihexyl borate, trihexylene glycol lbiiborate, and tri(m, p, cresyl) borate with a mixture of at least two chlorides of metals selected from the group consisting of Ti(IV), Zr(IV), Hf(IV), Sn(IV), Al(III), Fe([ll), Mo(V), Ta(V), and W(VI) together with the complex compounds formed thereby.

I claim:

'1. The method which comprises mixing at least one substantially anhydrous borate ester selected from the group consisting of trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, trihexyl borate, trihexylene glycol biborate, tri (m, p cresyl) borate, and trimethoxyboroxine with a first substantially anhydrous chloride of a metal selected from the group consisting of Ti (IV), Zr (IV), Hf (IV), Sn (IV), A1 (111), Fe (III), Ga (III), In (III), Mo (V), Nb(V), Ta (V), and W (VI) in a molar ratio of at least 0.33 mole of the selected Iborate for each mole of the chloride of the first selected metal in an inert substantially anhydrous diluent, permitting the chloride of the first selected metal to react with the selected borate at a temperature between room temperature and about 200 C. until the reaction mixture ceases to give oil organic chloride thereby forming a liquor comprising said diluent and a compound of complex chemical structure comprising the first selected metal, boron, carbon, hydrogen, chlorine, and oxygen, mixing with said liquor the chloride of a second selected metal selected from said group and permitting it to react with said compound at a temperature. between room temperature and about 200 C. until the reaction mixture ceases to give off an organic chloride thereby forming a second liquor comprising said diluent and a second compound of complex chemical structure comprising the selected metals, boron, carbon, hydrogen, chlorine, and oxygen, the molar quantity of the chloride of the second selected metal being not greater than the molar quantity of the chloride of the first selected metal.

2. The method as claimed by claim 1 wherein the diluent is selected from the group consisting of the selected borate, methylene chloride, chloroform, and carbon tetrachloride.

3-. The compound of complex chemical structure produced by the method claimed by claim 1 after removal of volatile material from said second liquor.

4. The method which comprises mixing substantially anhydrous trimethyl borate with a first substantially anhydrous chloride of a metal selected from the group consisting of Ti (IV), Zr (IV), Hf (IV), Sn (IV) Al (III), Fe (III), Ga (III), In (III), Mo (V), Nb (V), Ta (V), and W (VI), in a molar ratio of at least 0.33 mole of said borate for each mole of the chloride of the first selected metal in an inert substantially anhydrous diluent, permitting the chloride of the first selected metal to react with said borate at a temperature between room temperature and about C. until the reaction mixture ceases to give. off methyl chloride thereby forming a liquor comprising said diluent and a compound of complex chemical structure comprising the first selected metal, boron, carbon, hydrogen, chlorine, and oxygen, mixing with said liquor the chloride of a second selected metal selected from said group and permitting it to react with said compound at a temperature between room temperature and about 120 C. until the reaction mixture ceases to give off methyl chloride thereby forming a second liquor comprising the selected metals, boron, carbon, hydrogen, chlorine, and oxygen, the molar quantity of the chloride of the second selected metal being not greater than the molar quantity of the chloride of the first selected metal.

5. The method as claimed by claim 4 wherein the diluent is selected from the group consisting of the trimethyl borate, methylene chloride, chloroform, and carbon tetrachloride.

6. The compound of complex chemical structure produced :by the method claimed by claim 4 after removal of volatile material from said second liquor.

7. The method as claimed by claim 4 wherein the chloride of one selected metal is iron trichloride.

8. The method as claimed by claim 4 wherein the chloride of one selected metal is titanium tetrachloride.

9. The method as claimed by claim 4 wherein the chloride of one selected metal is molybdenum pentachloride.

10. The method as claimed by claim 4 wherein the chloride of one selected metal is tungsten hexac-hloride.

11. The method as claimed by claim 4 wherein the chloride of one selected metal is aluminum trichloride.

12. The compound of complex chemical structure, produced by the method claimed !by claim 7 after removal of volatile material from said second liquor.

13. The compound of complex chemical structure produced by the method claimed by claim 8 after removal of volatile material from said second liquor.

Cir

14. The compound of complex chemical structure produced by the method claimed by claim 9 after re- 1 moval of volatile material from said second liquor.

15. The compound of complex chemical structure produced by the method claimed by claim .10 after removal of volatile material from said second liquor.

16. The compound of complex chemical structure produced by the method claimed by claim 11 after -T6-i moval of volatile material from said second liquor.

References Cited OTHER REFERENCES Steinberg, Organoboron Chemistry, Intersc. PubL, John Wiley and Sons, Inc., NewYork (1964), vol. 1 (pp. 14446, 530) ,TOBIAS E. LEVOW, Primary Examiner H. M. S. SNEED, Assistant Examiner U.S. Cl. X.R. 

